Solutions for enhancing the effectiveness of insecticides and fungicides on living plants and related methods

ABSTRACT

The present invention relates to a solution for resisting destruction of living plants and a related method. A solution including a buffered amine oxide admixed with at least one material selected from the group consisting of insecticides and fungicides is applied to the living plant and provides a synergistically effective greater resistance to living plant deterioration than any of the individual buffered amine oxide, insecticides and fungicides achieve. A related method is disclosed.

CROSS REFERENCE TO RELATED APPLICATION

The present application is a 35 U.S.C. § 371 national phase from PCTInternational Application No. PCT/US2019/037851, filed Jun. 19, 2019which is a Continuation of U.S. Continuation-in-part application Ser.No. 16/208,976, filed on Dec. 4, 2018, now U.S. Pat. No. 10,952,433,issued Mar. 23, 2021, which is a continuation-in-part of U.S.application Ser. No. 14/674,465, filed on Mar. 31, 2015 and is entitled“SOLUTIONS FOR ENHANCING THE EFFECTIVENESS OF INSECTICIDES ON LIVINGPLANTS AND RELATED METHODS,” the contents of each of which areincorporated herein by reference in their entirety.

BACKGROUND OF THE INVENTION 1. Field of the Invention

The present invention relates to an improved solution for enhancingprotection of living plants through synergistic effects between bufferedamine oxides and insecticides and fungicides and related methods.

2. Description of the Prior Art

Fungi, insects and other pests cause significant economic losses in foodcrop production as well as losses in forestry, tree plantations,pastures, flowers and other agricultural products. In addition,fungicide and insecticides have been employed in a wide variety oflocations and types of uses to inhibit plant destruction due to fungusand insect pests. Problems created by insects and fungi have longexisted in many environments including, but not limited to agriculture,parks, golf courses, residential environments, highways, vegetablegardens, railroad tracks, recreational facilities, floral gardens,forests, pastures, waterways and in many other environments. This caninterfere with desired functionality, the health of plants, as well asthe aesthetics of an area containing vegetation.

It has been known to use a wide variety of materials to protect livingplants from insects and fungi. A wide variety of insecticides andfungicides have been employed in order to enhance the health of livingplants and resist attack thereon by insects, fungi and other destructiveorganisms.

It has been known to introduce wood preservatives into lumber in orderto resist deterioration of the same.

Ward, U.S. Pat. No. 7,896,960 discloses a method and solution forproviding enhanced penetration of wood preservatives into wood to agreater depth through synergism between a buffering agent and an amineoxide. It contemplates the use of various types of wood preservatives onwood which has been severed from a living tree. Green lumber is alsosaid to be treatable by the system.

This patent, which relates to wood as distinguished from living plantsdoes include within the definition of wood preservatives, a number ofchemical compounds including specific reference to fungicidal,insecticidal, water resistant, termite resistant materials.

U.S. Pat. No. 6,811,731 is directed toward a fire-retardant wood-basedcomposite created by treating a green wood furnish with aphosphate/borate fire-retardant material. The fire-retardant treatedgreen wood furnish is blended with a binder and then bound by applyingpressure to form a non-leaching fire retardant wood based composite.

Walker, U.S. Pat. No. 6,572,788 discloses the use of amine oxides aswood preservatives. It states that the amine oxides inhibit microbialgrowth in wood. This patent relates to wood which has been severed fromgrowing trees and discloses the use of wood preservatives which are saidto inhibit destructive organisms such as fungi and sapstain, forexample. It is directed toward preserving structural integrity of woodafter the tree has been killed and resisting destruction of theresultant lumber as the prime objective.

Tseng, U.S. Pat. No. 6,508,869 discloses the use of amine oxides toenhance the performance of boron compounds as wood preservatives. Thereis mention of the amine oxides improving the effectiveness of boroncompounds as insecticides or biocides and plant growth regulatingagents. They are also said to provide better dispersion of boroncompounds when applied to plants and fungi. It also makes reference tothe seeds of plants and the area on which the plants or fungi grow.

There remains, therefore, a very real and substantial need for animproved system for resisting attacks on and destruction of livingplants by insects and fungi.

SUMMARY OF THE INVENTION

The present invention provides a solution and method of obtainingsynergistic action between a fungicide and a buffered amine oxide and/oran insecticide and a buffered amine oxide in order to provide enhancedresistance of a living plant to undesired deterioration due to fungi andinsects.

The solution and related method provides for greater plant protectionthan would be obtained through use of the fungicide alone or theinsecticide alone.

It is an object of the present invention to provide effective economicalmeans for enhancing the performance of insecticides and fungicides onliving plants.

It is another object of the present invention to provide a solution andrelated method which will enhance the performance of fungicides andinsecticides on living plants.

It is another object of the present invention which, through synergismwith a buffered amine oxide, enhances the performance of conventionalinsecticides and fungicides.

It is yet another object of the present invention to employ asynergistic combination of insecticides or fungicides with a bufferedamine oxide system to produce improved insect and fungi resistance whileemploying a smaller quantity of the insecticide or fungicide.

These and other objects of the invention will be more fully understoodfrom the following description of the invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

As employed herein, the term “living plant” is used in its ordinarysense, and is to be distinguished from both (a) plants which have diedand (b) products or items which once were, but are no longer living orpart of a living plant such as, for example, lumber. This definitionwill include living plant food products such as fruits or vegetableswhich have been removed from a plant.

Living plants are characterized by the following:

-   -   (a) they secure energy from light, water and carbon dioxide, or        from pre-existing carbon-based life forms, or from other forms        of energy;    -   (b) they can grow through either reproductive cells and or        evolutionary specialized cells that can differentiate into other        kinds of cells to perform different functions;    -   (c) they have structures that allow them to resist loss of        water, allow movement of water, allow movement of materials        (such as sugars, minerals, hormones, wastes and microelements as        examples), resist environmental forces (such as UV light,        freezing and thawing, desiccation, submersion, blowing        particles, fire, animal digestion, toxins and altitudes as        examples);    -   (d) they conduct biochemical metabolic functions to live, grow,        and reproduce through many types of cells or organelles that are        designed by actively operating DNA, enzymes and other        biologically active molecules;    -   (e) they compete for resources from other plants and other        living organisms; and    -   (f) they die through natural or manmade forces.

As employed herein, a “buffer” or “buffer system” is an aqueous solutionconsisting of a mixture of a weak acid and its conjugate base or a weakbase with its conjugate acid. A buffer system may also be obtained byadding a weak acid/conjugate base or a weak base/conjugate acid or byadding the weak acid/weak base and a strong acid/strong base insufficient amount to form the conjugate acid/conjugate base.

A buffer is a solution that resists change in pH when an acid or base isadded to it. A “single buffer” involves only one compound being added toa solution to make a buffer which internally contains a weak acid andits conjugate base or a weak base and its conjugate acid. A “dual buffersystem” or “dual buffer” consists of two different buffering agents eachof which has its own weak acid/conjugate base or weak base/conjugateacid or weak acid/weak base pairs which combine to provide the desiredpH. The specific buffering system or buffers of the present inventionare preferably all dual buffering systems or dual buffers.

The present invention involves creating a synergistic effect by applyingto the plant a solution which includes of either an insecticide or afungicide or both which will achieve a synergistically createdimprovement in the result through combining the same with a bufferedamine oxide.

The amine oxides may be mixed with buffers in a solvent to create abuffered amine oxide solution and then mixed with an insecticide and/orfungicide solution. The preferred amine oxides are selected from thegroup consisting of (a) the 12 carbon length amine oxides such as thatsold under the trade designation Barlox 12 and (b) a mixture of the 12and 18 carbon lengths sold under the trade designation Barlox 1218. Thebuffer system has the property that the pH of the solution changes verylittle when a small amount of a strong acid or strong base is added toit. Buffer solutions are employed as a means of keeping pH at a nearlyconstant value within a wide range of chemical operations. In thepresent invention, the buffer system helps to maintain a substantiallyconstant pH when in contact with biological systems, such as livingplants.

The buffer system concepts can be extended to polyprotic species inwhich one or more protons may be removed to form different buffersystems, i.e., phosphate systems. Among the preferred buffers areammonium salt/ammonia, Deprotonated Lysine/Doubly Deprotonated Lysine,Phosphate Dibasic, Potassium Bicarbonate/Potassium Carbonate.

Boric Acid/Borax, Potassium Phosphate Dibasic/Potassium PhosphateTribasic, Ammonium Citrate Tribasic, and Potassium PhosphateMonobasic/Potassium Phosphate Dibasic.

It will be appreciated that the buffered amine oxides do notsignificantly alter the pH of the insecticide or fungicide products but,rather, make the pH much less likely to change based on the buffercapacity of the buffer additives.

A series of tests were performed in the United States in order todetermine the effectiveness of a solution of the present inventioncombining an insecticide with a dual buffered amine oxide and theeffectiveness of a solution of the present invention combining afungicide with a buffered amine oxide.

TABLES 1-3 describe, respectively, describe the buffer systems employedin the North American experiments reported in TABLES 4 and 5, with TABLE2 referring to the experimental method and TABLE 4 showing a group ofbuffer systems pH and total Ion strengths.

TABLE 1 recites the composition of buffer systems 3-4 that were used inthe studies. Buffer systems 3-4 were prepared by dissolving theappropriate reagents into one liter of deionized water until ahomogenous solution was obtained. TABLE 4 shows, in the left handcolumn, the number assigned to a particular buffer with column 2containing the abbreviated name or full name of the buffers. The amountof acidic chemical per liter and basic chemical per liter appear in thenext two pairs of columns.

TABLE 1 Buffer Systems 3, 4 Composition Acidic Chemical Basic ChemicalBuffer Buffer System Name (per liter) (per liter) No. (Abbreviated Name)Amount Name Amount Name 3 Potassium Phosphate 0.5 mol Potassium 0.5 molPotassium Monobasic/Potassium Phosphate Phosphate Phosphate DibasicMonobasic Dibasic (Phosphate Buffer 1) 4 Potassium 0.5 mol Potassium 0.5mol Potassium Bicarbonate/Potassium Bicarbonate Carbonate Carbonate(Carbonate Buffer)

TABLE 2 is directed toward the experimental method in preparation of thepre-blended amine oxide and buffer systems. The compositions of buffersystem identifies the buffer system name in the first column with thenext two columns providing identification of the acidic chemical andweight percent amount followed by the amount of basic chemical and thename. The last two columns provide, respectively, the water weightpercent and Barlox 12 (30% by weight amine oxide donor) weight percent.

TABLE 2 discloses the composition of pre-blended Amine Oxide and BufferSystem 3 that was used in the studies. Buffer system 3 was prepared bydissolving the appropriate reagent salts in water and then adding theamine oxide donor in sufficient amount to make one liter of solution.

TABLE 2 Pre-blended Buffer System 3 Composition Barlox 12 (30% by weightamine oxide) Acidic Chemical Basic Chemical Water Amine oxide BufferBuffer System Name Amount Amount Amount Donor Letter (Abbreviated Name)(wt %) Name (wt %) Name (wt %) (wt %) 3 Potassium Phosphate 4.36Potassium 3.13 Potassium 12.51 80.00 Monobasic/Potassium PhosphatePhosphate Phosphate Dibasic Monobasic Dibasic (Phosphate Buffer 3)

TABLE 3 shows the pH and buffer total Ion strengths (Molar) for buffersystems 3 and 4.

TABLE 3 Buffer System pH and Total Ion Strengths pH Buffer Total BufferBuffer System Name (Buffer Ion Strength No. (Abbreviated Name) System)(Molar) 3 Potassium Phosphate 6.8 1.05M Monobasic/Potassium PhosphateDibasic (Phosphate Buffer 1 ) 4 Potassium Bicarbonate/ 10.2 0.995MPotassium Carbonate (Carbonate Buffer)

Referring to TABLES 4 and 5, the columns under the heading BufferedAmine Oxide System correspond to the identification provided in TABLES 1through 3.

In general, in the present invention, amine oxides were mixed withbuffers and then added to insecticide or fungicide formulations. Amongthe preferred amine oxides were those of 12 carbon length such as thatsold under the trade designation Barlox 12 and a mixture of the 12 and18 carbon lengths sold under the trade designation Barlox 1218. Thebuffer solution serves to stabilize the pH at a nearly constant value ina wide variety of chemical operations.

In the present invention, the buffer system maintains a substantiallyconstant pH when in contact with biological systems. The buffer systemis an aqueous system consisting of a mixture of a weak acid in itsconjugate or a weak base in its conjugate acid. One may obtain thedesired buffer system by directly adding the weak acid/conjugate base orweak base/conjugate acid salts or by adding the weak acid/weak base anda strong acid/strong base in sufficient amount to form the conjugateacid/conjugate base.

The amine oxide additives may be mixed as tank blends with theinsecticides or fungicides or may be incorporated into the insecticidesor fungicide formulas.

TABLE 1 shows 2 different buffers, while TABLE 3 shows an amine oxideblend. TABLE 4 discloses systems wherein the appropriate reagents weredissolved in deionized water until a homogenous solution was obtained.TABLE 3 deals with the pre-blending of the amine oxide and buffersystems with the appropriate reagents salts dissolved in water andsubsequently, adding the amine oxide donor.

Except where the fungicide or insecticide is listed in column 1 of thetable and identified by concentrations in terms of PPM which involvestotals of the amount present on the basis of total solution weight, withrespect to the other columns of the table refer to concentration on atotal solution volume basis.

In employing the tests which generated the data recited in Table 4, awater control employing twenty seedlings 20 milliliters per seedling oflow volume hand spray showed 100% staining fungi in the stem wound asindicated in the first number in the last column of Table 4. The buffersand amine oxide employed are shown in Tables 1 through 3. Protocolinvolved seven days after application, a sterile razor blade wound ofabout 2 millimeters by 10 millimeters was established on each seedlingstem. Fourteen days after the stem wounding, wounds were examined forthe presence of staining fungi. In creating these for solution were usedthe buffer and amine oxides were added to the dilute solution offungicide.

American Field Tests of Buffered Amine Oxide Additives to Fungicide andInsecticide (Tables 4 and 5)

TABLE 4 May to Jun. 2013 Buffered Amine Oxide System Fungicide TypeBuffer Number & Amine Oxide Percent of Seedlings Product ConcentrationDonor or Letter with Staining PPM No Buffer 3 4 Fungi in StemPropiconazole 12 1218 12 1218 12 1218 Wound of White Oak 100⁽¹⁾⁽²⁾ 200:1100 400:1 100 200:1 100 400:1 100 200 PPM  20 100 PPM  80 50 PPM 100 50PPM 200:1 0 50 PPM 400:1 20 50 PPM 200:1 0 50 PPM 400:1 0 200:1 100400:1 100 200:1 100 400:1 100 50 PPM 200:1 0 50 PPM 400:1 20 50 PPM200:1 0 50 PPM 400:1 0 200:1 100 400:1 100 200:1 100 400:1 100

Referring to TABLE 4 wherein a commonly used fungicide, Propiconazolewas employed in tests in the amount of 50:200 PPM (parts per million)employed with and without buffered amine oxides systems 3 and 4 withsome of the tests employing the 12 carbon length and others, the 1218carbon mixture. In a preferred embodiment in 1218 on a weight basis, the12 carbon length will be present in an amount of about 1.3 to 2.0 timesthe amount of 18 carbon length and in the preferred range about 1.5 to1.8 times the amount of 18 carbon length. The tests were performed onwhite oak seedlings which were provided with a stem wound in which wasintroduced staining fungi which was of the ceratocystis variety.Staining indicates that the fungicide or other treatment did not resistgrowth of the fungi with the number 100 representing 100% with noinhibitions of fungi growth and the number 0 indicating 0% or 0indicating no fungi growth.

Referring in TABLE 4 to the heading under No Buffer, it is seen that theamine oxides of both the 12 and 1218 length in concentrations of 200:1and 400:1 did not in any way inhibit growth of the staining fungi.Considering the Propiconazole employed alone, it is seen that with 50ppm, 100 ppm and 200 ppm, the inhibition at 50 ppm did not exist asthere was 100% growth and that at 100 ppm, 80% growth was experienced,while at 200 ppm, 20% growth existed.

With continued reference to TABLE 4, the combination of the fungicidewith the buffered amine oxide system No. 3, employing 50 ppm in the 12carbon length combined with 50 ppm propiconazole, at 200:1concentration, there was 0 fungal growth, and at 400:1, there was 20%growth. The same 50 ppm of the fungicide employed with 200:1 and 400:1,1218 buffered amine oxide system No. 3, produced 0 fungal growth.

TABLE 4 shows that both the 12 and 1218 length of buffered amine oxidesystem No. 3 used alone at concentrations of 200:1 and 400:1 produced nofungal growth inhibition as both showed 100% staining fungi.

Considering buffered amine oxide system No. 4 when the 12 length is usedin combination with 50 ppm of the fungicide, in concentration of 400:1,20% fungal growth was experienced and in 200:1, no fungal growth wasexperienced. With regard to the fungicide being in 50 ppm and the 1218carbon length, a buffered amine oxide system No. 4, as to both 200:1 and400:1 concentration, there was 0 fungal growth.

Considering both the 12 length and 1218 length employed without thefungicide in both concentrations, 200:1 and 400:1, there was a 100%fungal growth.

The test results in TABLE 4, therefore, support the conclusion that, inthe absence of a buffer, there was 100% fungal growth. In the use of 12length amine oxide or 1218 length amine oxide alone with both bufferedamine systems No. 3 and 4, there was 100% fungal growth. When, however,the combination of fungicide and the buffered amine oxide systems wereemployed, whether length 12 or 1218 was considered, when theconcentration was 200:1, there was no fungal growth and when theconcentration was 400:1, there was 20% fungal growth.

The method of testing the materials was to spray the trunk of theseedling with the particular solution being tested and 7 days after suchapplication, creating a wound of approximately 2 millimeters by 10millimeters on each seedling stem. Fourteen days after the wounding, thewounds were examined for the presence of staining fungi.

TABLE 5 May to Jun. 2013 Buffered Amine Oxide System Insecticide TypeBuffer Number & Amine Oxide Product Concentration Donor or LetterPercent Gypsy Moth Caterpillar PPM No Buffer 3 4 Damage to White OakPermethrin 12 12 12 1 Month After Application 100⁽¹⁾⁽²⁾ 200:1 100 400:1100 100 PPM  0 50 PPM 30 10 PPM 80 10 PPM 200:1 0 10 PPM 400:1 10 200:1100 400:1 100 10 PPM 200:1 0 10 PPM 400:1 10 200:1 100 400:1 100

Referring to TABLE 5, there is shown the results of testing of aninsecticide which, in this case, was permethrin, which was presented invarious tests in quantities of 10 ppm to 50 ppm and 100 ppmconcentrations were tested against a control with no buffer as well asbuffer amine oxide systems employing 12 length carbon.

The particular solutions tested were applied to a stem of the white oakseedling using a low volume hand spray and spraying 20 milliliters perseedling. A total of 20 seedlings were tested. The use of permethrinalone in concentration of 10 ppm resulted in 80% gypsy moth caterpillardamage. At permethrin concentration of 50 ppm, the damage after onemonth was 30% and with 100 ppm used alone, the damage was 0. Whenbuffered amine oxide system No. 3 was employed in concentrations of400:1 with 10 ppm of the insecticide, the gypsy moth caterpillar damagewas 10% and when a concentration of 200:1 was employed with 10 ppminsecticide, the damage was 0. This shows that a much smaller amount ofinsecticide was needed to achieve 0 damage when was used in combinationwith the buffered amine oxide system which created a desired synergisticeffect. If less than 50 percent of the leaf mass was eaten, this showssuccessful inhibition of gypsy moth damage.

Using buffered amine oxide system No. 3 alone in concentrations of 400:1and 200:1 resulted in 100% gypsy moth caterpillar damage after onemonth.

Using buffered amine oxide system No. 4 in combination with 10 ppm ofthe insecticide, reduce the gypsy moth caterpillar damage to 10% whenusing a concentration of 400:1 and to 0 when using a concentration of200:1.

Using buffered amine oxide system No. 4 without the insecticide resultedin 100% gypsy moth caterpillar damage.

The foregoing tests show that neither buffered amine oxide system 3 nor4 in concentrations of 200:1 and 400:1 produced any measurabledifference in gypsy moth caterpillar damage over the control which hadneither insecticide nor buffered amine oxide systems. When, however, thebuffered amine oxide systems 3 and 4 were employed with insecticideconcentrations of 10 ppm, at 400:1 concentration of the 12 length carbonbuffered amine oxide systems, there was only 10% gypsy moth caterpillardamage and with 200:1 concentration, there was 0 damage.

If desired, a single solution may contain both an insecticide and afungicide.

Extensive additional testing of a wide variety of fungicides was done inan effort to confirm the performance of the present invention. The datais presented in Table 6.

In performing the tests employing ten red oak seedlings per iterationwith the materials being tested applied at approximately 12 millilitersper seeding applied with a low volume hand spray. The red oak (Quercusrubra) was then tested during the period of Aug. 28, 2017 through Oct.5, 2017 in suburban Pittsburgh, Pa. in assignee's agriculturalgreenhouse. All fungicides employed in the test were registered by theUnited States environmental protection agency for use as pesticides.Seven days after application, a sterile razor blade wound ofapproximately 2 millimeters by 10 millimeters was created on eachseedling stem Immediately after, the wounding 1 ml of macerated fungalblend suspended in distilled water was applied to each stem wound.Twenty-eight days after wounding, the wounds were evaluated for anaverage percentage of staining fungi present in each seedling stemwound. Opaque black straw covering was applied to each wound. The opaqueblack straws were applied within about one minute after wounding andinoculation with the fungi. The straws are simple polypropylene strawsas employed in the food industry, for example. They are wider than thenormal straws as they are employed in the health industry for patientsneeding such straws. They are sterile. The purpose for using such strawsis to facilitate the creation of a dark environment on the wound asfungi tend to like dark damp places. This is employed to enhance theeffectiveness of the test by accelerating the severity of the fungalgrowing conditions. Each stem wound was given two ml of distilled water10, 17, 21 and 28 days after wounding by a low volume trigger spray. Allsolutions were included a porpylene glycol based dye at a concentrationof 100:1. The greenhouse conditions were maintained at 65° F. to 85° F.and the humidity range of 30 to 80% relative humidity. The test whichemployed the combination of thiabendazole, fludioxonil and azoxystrobinwas obtained as a formulated pesticide product which was available underthe trade designation “Sporgard”.

It will be appreciated from the following analysis and the data whichcontains the results of testing a large number of fungicides withvarious quantities and with various combinations of materials includingthe preferred composition of the present invention. Among the preferredfungicides which were tested are Thiabendazole, Fludioxonil,Azoxystrobin, Chlorothalonil, Propiconazole, Mancozeb, Vinclozolin, andMefenoxam.

The resulting conclusion as demonstrated by the tests results is thatapplicant's invention permits the use of substantially less fungicides,while achieving equal or better results. This can contribute to the enduser saving money.

The general format of tables 6 through 8 will involve the first columnidentifying the absence of or quantity of a fungicide or identity of thefungicide as well as controls. The use in column 1 of “(No WaterControl)” means that neither water nor dye were employed. The use of“(No Dye Control)” means that there was no dye employed with only waterbeing employed as a control. The dye when used was added to show thatthe test article was adequately covered in the needed area with the samevolume of treatment. The controls also function to confirm that noinfluences from inert coformulants occurred. The second column willindicate the quantity in parts per million of the fungicide employed.With the third through fifth columns involve concentrations of 200:1.The third column will identify concentrations of the chosen buffersystems which in this series of tests were buffer systems 3 and 4 asdefined in Tables 1 through 3.

The third column which deals with two buffer systems, but no amineoxide.

The fourth column employs amine oxides without a buffer. The fourthcolumn deals with the amine oxide without a buffer.

The fifth column deals with the use of buffered amine oxide system andbuffer identity. The final column is a numerical grade which representsthe percent of staining fungi coverage in percentage in the stem woundof the red oak seedlings as measured on day 28.

TABLE 6 Buffered Amine Oxide System Buffer Number & Amine Oxide Donor orLetter Product No Amine Oxide Amine Oxide Buffer System Buffer SystemConcentration Buffer System Buffer System (No Buffer) 4 3 Percent ofFungicide Type PPM 4 3 12 1218 12 1218 12 1218 Staining Fungi NoFungicide 0 64 No Fungicide 0 200:1 85 No Fungicide 0 200:1 67 NoFungicide 0 200:1 77 No Fungicide 0 200:1 56 No Fungicide 0 200:1 61 NoFungicide 0 200:1 69 No Fungicide 0 200:1 78 No Fungicide 0 200:1 94 NoFungicide 0 77 (No water Control) No Fungicide 0 54 (No Dye Control)Thiabendazole, Fludioxonil, 160 72 Azoxystrobin Thiabendazole,Fludioxonil, 160 200:1 92 Azoxystrobin Thiabendazole, Fludioxonil, 160200:1 59 Azoxystrobin Thiabendazole, Fludioxonil, 160 200:1 19Azoxystrobin Thiabendazole, Fludioxonil, 160 200:1 25 AzoxystrobinThiabendazole, Fludioxonil, 160 200:1 36 Azoxystrobin Thiabendazole,Fludioxonil, 160 200:1 26 Azoxystrobin Thiabendazole, Fludioxonil, 32040 Azoxystrobin Thiabendazole, Fludioxonil, 640 22 AzoxystrobinChlorothalonil 1235 91 Chlorothalonil 1235 200:1 41 Chlorothalonil 1235200:1 72 Chlorothalonil 1235 200:1 64 Chlorothalonil 1235 200:1 55Chlorothalonil 1235 200:1 24 Chlorothalonil 1235 200:1 27 Chlorothalonil1235 200:1 33 Chlorothalonil 1235 200:1 33 Chlorothalonil 2470 49Chlorothalonil 4940 37 Propiconazole 100 85 Propiconazole 100 200:1 77Propiconazole 101 200:1 74 Thiabendazole, Fludioxonil, 160 200:1 67Azoxystrobin Thiabendazole, Fludioxonil, 160 200:1 52 AzoxystrobinPropiconazole 102 200:1 43 Propiconazole 103 200:1 55 Propiconazole 104200:1 13 Propiconazole 105 200:1 20 Propiconazole 106 200:1 33Propiconazole 107 200:1 44 Propiconazole 200 81 Propiconazole 400 33Mancozeb 1097 74 Mancozeb 1097 200:1 77 Mancozeb 1097 200:1 67 Mancozeb1097 200:1 58 Mancozeb 1097 200:1 30 Mancozeb 1097 200:1 9 Mancozeb 1097200:1 24 Mancozeb 1097 200:1 23 Mancozeb 1097 200:1 30 Mancozeb 2194 35Mancozeb 4388 22 Vinclozolin 122 43 Vinclozolin 122 200:1 55 Vinclozolin122 200:1 49 Vinclozolin 122 200:1 32 Vinclozolin 122 200:1 16Vinclozolin 122 200:1 7 Vinclozolin 122 200:1 17 Vinclozolin 122 200:134 Vinclozolin 122 200:1 38 Vinclozolin 244 21 Vinclozolin 488 15Mefenoxam 20 64 Mefenoxam 20 200:1 55 Mefenoxam 20 200:1 52 Mefenoxam 20200:1 38 Mefenoxam 20 200:1 25 Mefenoxam 20 200:1 14 Mefenoxam 20 200:116 Mefenoxam 20 200:1 25 Mefenoxam 20 200:1 21 Mefenoxam 40 42 Mefenoxam80 23

Referring more specifically to Table 6 (pages 14-17) with reference tothe first nine entries wherein no fungicide was employed, it is seenthat where buffer systems 4 and 3 were employed without an amine oxidein concentrations of 200:1, the scores were 67% and 85%.

As to the amine oxide without buffer and carbon lengths of 12 and 1218,the percentages were respectively 77 and 56. As shown in the next columnemployed the buffered amine oxide system of the present invention. Bothbuffered amine oxide and buffer 4 or buffer 3, each with carbon lengthsof either 12 or 1218 were employed. Staining percentages were 61 and 78with respect to buffer system 4 with the 12 carbon length performingbetter than the 1218 carbon length. Also, with respect to buffer system3 in combination with the amine oxide, the percentage was 69 withrespect to 12 carbon length and 94 with respect to 1218 carbon length

In summary, on the basis of the absence of use of any fungicide, thepercentage stain varied from a low of 56 to a high of 94.

Referring to Table 6, tests were performed employing a combination ofThiabendazole, Fludioxonil, Azoxystrobin, which combination is offeredcommercially under the trade designation “Sporgard” with a compositionof 19.04% Thiabendazole, 19.04% Azoxystrobin and 1.92% Fludioxonil,Propiconazole, Mancozeb, Vinclozolin and Mefenoxam. In all but the lasttwo tests employing this combination, a 160 ppm (parts per million)based on total solution weight was employed. It is noted when it wasemployed alone the fungi covering was 72. With the fungicide and noamine oxide and the buffer systems 4 and 3, respectively, were at 92 and67.

The amine oxide without buffer in lengths of 12 and 1218 produced 52 and59 staining Buffer system 4 in combination with the buffered amine oxidein lengths of 12 and 1218, respectively, produced 19 and 36 which was asubstantial improvement over the other preceding categories without theamine oxide or without the buffer. Similarly, the buffered amine oxideemploying buffer system 3 with 12 and 1218 carbon length produced 25 and26 respectively.

With the two tests employing the fungicide in increased amounts of 320ppm and 640 ppm, without any of the other materials, the results wererespectively 40 and 22. These series of tests show that successfulresults can be obtained while using the fungicide in the amount of 160ppm with the buffered amine oxides system of the invention producingcomparable results while permitting a reduction in the amount offungicide employed.

In Table 6, results of the use of chlorothalonil were compared. Thechlorothalonil in amount of 1235 ppm used alone resulted in a veryunsatisfactory 91 staining fungi coverage. When it was employed in thesame quantity with no amine oxide, but buffer concentrations of 200:1for buffer systems 4 and 3, respectively, the results were 41 and 72.Testing the same fungicide with 200:1 concentration of the fungicidewith amine oxides with no buffer, the results were respectively 64 and55 staining.

The chlorothalonil fungicide employed with buffered amine oxideemploying buffer system 4 and the fungicide concentration of 200:1 andcarbon length of 12 and 1218 produced good results of 24 and 33,respectively. The buffered amine oxides system employing buffer system 3and carbon lengths 12 and 1218, respectively, produced results of 27 and33. When the chlorothalonil fungicide was used alone in the amount of2470 ppm, the percent of staining was 49 and when 4940 ppm was employed,the percent staining was 37. As a result, the use of the uniquecombination of the invention produced superior stain fungi coverageresistance when 1235 ppm of the fungicide was used compared with the useof the fungicide alone in much greater quantities. These tests confirmedthe fact that one may get superior results with the formulation of thepresent invention employing a reduced amount of fungicide as comparedwith (a) the fungicide employed alone, and (b) when the buffer was usedwithout the amine oxide and when the amine was used without the buffer.

Table 6 also provides test results employing the fungicidePropiconazole. When the propiconazole was used alone, the percentage ofstaining was 85. Employing the buffer systems 4 and 3 without amineoxide, resulted in staining percentage, respectively, at a concentrationof 200:1 of 77 and 74. Use of amine oxide without a buffer in lengths 12and 1218, showed staining percentage of 43 and 55, respectively.

Employing the buffered amine system 4 in carbon lengths of 12 and 1218,respectively, produced results of 13 and 33. Employing the bufferedamine oxide system with buffer system 3 and lengths 12 and 1218,produced staining at 20 and 44. It is noted that in these tests, theamount of propiconazole ranged from 100 ppm to 107 ppm and at 107, theresult was 44. Further increases in propiconazole to 200 ppm and 400 ppmproduced 81 and 33. This series of tests shows that employing theformulation of the invention with different buffer systems and carbonlengths of 12 and 1218 created successful staining fungi resistancecompared with substantially increasing the percentage propiconazolewithout employing the formulations of the present invention.

As shown in Table 6, tests were performed with the fungicide Mancozebwith all but the last two tests having a concentration of 1097 ppm.Fungicide concentration with no other ingredients, the percent stainingfungi was 74. When buffer systems 4 and 3 were employed without amineoxide, the numbers were respectively, 77 and 67. When the same quantityof Mancozeb was employed with amine oxide with no buffer, the 12 and1218 carbon lengths performed at 58 and 30.

When the buffered amine oxide system of the present invention wasemployed, buffer system 3 had values of 24 and 30 and buffer system 4with lengths 12 and 1218, respectively, had values of 9 and 23. When theconcentration of mancozeb was increased to 2194 ppm and 4388 ppm, thenumbers were 35 and 22. These numbers, respectively, were not any moreeffective and generally less effective than the fungicide employed at1097 ppm. As a result, it is apparent that a smaller quantity offungicide may be employed when it is used with the buffered amine oxidesystems of the present invention.

With no buffer or amine oxide, the result was 43 and when the fungicide,Vinclozolin, was employed at 122 ppm, with no amine oxide, the resultswere 55 and 49 with the formulation being 200:1. When it was employedwith amine oxide, but no buffer in the carbon lengths 12 the percentageof staining was 32 and in carbon lengths 1218, it was 16.

Use at this level with 200:1 concentration and buffer system 4 at carbonlength 12 and carbon length 1218, produced results of 7 and 34. Buffersystem 3 producing results, respectively, of 17 and 38. When the amountof Vinclozolin was increased to 244 ppm, which is double that of thenext preceding test result, and 488 ppm, the results were respectively21 and 15. As a result, this data with Vinclozolin establishes the factthat with the buffered amine oxide system formulation of the presentinvention, substantially less fungicide can be employed with equal orbetter results in terms of percent of stain fungi.

In Tables 6, there is reported data from tests of Mefenoxam with all butthe last two tests employing 20 ppm of the fungicide. The othercomponents when employed were used in a concentration of 200:1. Themefenoxam alone produced a result of 64. Buffer systems 4 and 3,respectively, without amine oxide produced results of 55 and 52 andamine oxide system without the buffer in lengths 12 and 1218,respectively, produced results of 38 and 25. With the preferred bufferedamine system in carbon lengths of 12 and 1218, the results were 14 and25, respectively, and for buffer system 3 were 16 and 21, respectively.By contrast, doubling the mefenoxam to 40 ppm without the buffered amineoxide system, produced a result of 42 and mefenoxam at 80 ppm, withoutthe buffered amine oxide, produced a result of 23. These results confirmthe fact that employing the buffered amine oxide of the presentinvention permits the use of a much smaller quantity of fungicide withbetter or equivalent results.

In evaluating the test results, it is noted that the staining fungalinhibition was substantially better employing applicant's buffered amineoxide system with the preferred 4 and 3 buffer systems. It will also benoted that the 12 carbon length and 1218 carbon length both performedeffectively. In each instance, the buffered amine oxide system was moreeffective in inhibiting staining fungi over (a) the tests with nofungicide, (b) the tests with no amine oxide, and (c) the tests withamine oxide, but no buffer.

A series of tests involving exposure of living plants which had beentreated with a variety of insecticides and buffered amine oxide systemsof the present invention were conducted. These tests includedcomparative tests wherein no insecticide was used, tests where no amineoxide was used, tests where no buffer was employed, but carbon lengthsof 12 and 1218 were employed and, finally, where two different bufferedamine oxide systems of the present invention were employed with 12carbon length and 1218 carbon length. In all of these tests, when thedosage of the insecticide was increased by approximately 50% or 100%,these results reflect the use of only the insecticide.

TABLE 7 Buffered Amine Oxide System Buffer Number & Amine Oxide PercentLepidopteran Product No Amine Donor or Letter Damage to ConcentrationOxide No Buffer CO3 PO4 Romaine Lettuce Insecticide PPM CO3 PO4 12 121812 1218 12 1218 24 hr No insecticide 0 41.0 No Insecticide 0 200:1 32.5No Insecticide 0 200:1 42.5 No Insecticide 0 200:1 48.0 No Insecticide 0200:1 41.5 No Insecticide 0 200:1 28.0 No insecticide 0 200:1 45.0 Noinsecticide 0 200:1 47.5 No insecticide 0 200:1 60.0 No insecticide 055.0 (No water Control) No Insecticide 0 45.5 (No Dye Control)Chlorantranilopril 60 10.5 Chlorantranilopril 60 200:1 13.5Chlorantranilopril 60 200:1 9.0 Chlorantranilopril 60 200:1 9.0Chlorantranilopril 60 200:1 5.5 Chlorantranilopril 60 200:1 2.5Chlorantranilopril 60 200:1 4.0 Chlorantranilopril 60 200:1 2.5Chlorantranilopril 60 200:1 0.0 Chlorantranilopril 90 8.2Chlorantranilopril 120 8.5 Acephate 70 22.7 Acephate 70 200:1 31.0Acephate 70 200:1 20.0 Acephate 70 200:1 36.0 Acephate 70 200:1 28.0Acephate 70 200:1 11.5 Acephate 70 200:1 7.5 Acephate 70 200:1 4.5Acephate 70 200:1 1.0 Acephate 105 16.5 Acephate 140 13.0Methoxyfenozide 100 29.5 Methoxyfenozide 100 200:1 13.5 Methoxyfenozide100 200:1 22.0 Methoxyfenozide 100 200:1 28.0 Methoxyfenozide 100 200:113.0 Methoxyfenozide 100 200:1 8.0 Methoxyfenozide 100 200:1 7.5Methoxyfenozide 100 200:1 9.0 Methoxyfenozide 100 200:1 4.5Methoxyfenozide 150 43.0 Methoxyfenozide 200 23.5 Spinosad 30 28.5Spinosad 30 200:1 17.0 Spinosad 30 200:1 20.5 Spinosad 30 200:1 24.5Spinosad 30 200:1 22.5 Spinosad 30 200:1 12.5 Spinosad 30 200:1 10.0Spinosad 30 200:1 9.5 Spinosad 30 200:1 6.5 Spinosad 45 17.0 Spinosad 6019.0 Permethrin 10 77.0 Permethrin 10 200:1 80.5 Permethrin 10 200:183.0 Permethrin 10 200:1 77.5 Permethrin 10 200:1 72.0 Permethrin 10200:1 22.5 Permethrin 10 200:1 24.0 Permethrin 10 200:1 28.0 Permethrin10 200:1 21.0 Permethrin 15 78.0 Permethrin 20 90.0 Indoxacarb 50 47.0Indoxacarb 50 200:1 50.5 Indoxacarb 50 200:1 25.5 Indoxacarb 50 200:126.5 Indoxacarb 50 200:1 25.5 Indoxacarb 50 200:1 7.0 Indoxacarb 50200:1 7.5 Indoxacarb 50 200:1 7.0 Indoxacarb 50 200:1 8.0 Indoxacarb 7520.0 Indoxacarb 100 12.5

In a first group of tests, the results of which are shown in Table 7(pages 22-24), romaine lettuce plants two to three inches in height wereexposed to 10 milliliters of solution applied to each plant using a lowvolume trigger spray. With respect to containers 0-7, ten plants wereemployed per container, nine were treated and one was an internalcontrol. In containers M-H, ten plants per container were used, fivewere treated and 5 were internal controls. Each container was infestedwith 30 lepidopteran larvae between the 5^(th) and 6^(th) instardevelopment. Fifteen cabbage loopers (Trichoplusia ni) and 15 beetarmyworms (Spodoptera exigua) were used to infest the romaine lettuceplants. Visual evaluations for the average percentage total surface areadamage were taken 24 hours after infestation. Percentage damage wasevaluated by 5% increments for total damage across all plant leaves.

As indicated in the first column of Table 7, in some tests, noinsecticide was employed and there were two controls; a no water controland a no dye control. A wide variety of insecticides selected from thefollowing group were tested: Chlorantranilopril, Acephate,Methoxyfenozide, Spinosad, Permethrin, and Indoxacarb. The productconcentration is shown in PPM in column 2 Column 3 is divided into twosubunits, the first being CO₃ and the second, PO₄. In all instances incolumns 3, 4 and 5 and their sub-columns, the concentrations used were200:1. The fourth column employed amine oxide, but no buffer. The fifthcolumn shows the preferred buffered amine oxide system which employsboth amine oxide and a buffer. Two sub-columns each are represented forCO₃ and PO₄. The final column is a reading of the Percent LepidopteranDamage to the romaine lettuce plants after 24 hours.

A second series of tests involved romaine lettuce discs approximately ⅝inch in diameter. (L. sativa). The results are reported in Table 8. Theywere dipped in the treatment solution one second per disc. This testinvolved the 5/5 configuration, i.e., 5 treated and 5 untreated. Theinfestation involved either lepidopteran larvae at the 3^(rd) to 4^(th)instar development per container: four cabbage loopers (Trichoplusiani), and four beet armyworms (Spodoptera exigua) were employed. The testcontainers were placed in a dark humidity cabinet at 15° C. and 80%relative humidity. Visual evaluations of the average percent damage weretaken at 24, 48 and 72 hours after the initiation of infestation. Theresults are provided in the last column of Table 8. Damage was evaluatedin 5% increments based on total disc area.

In addition to testing the buffered amine system of the presentinvention with the two amine oxides identified as CO₃ and PO₄ and theiruse with 12 carbon length and a mixture of 12 and 18 designated 1218 forcomparative data purposes various differences were created in thetesting. Some of the tests were performed with (a) no insecticide alongwith (b) no amine oxide for CO₃ and PO₄ and (c) with no buffer, but withamine oxide. Also, tests were run using no insecticide and no watercontrol with no foliar application being made. Tests with no insecticideand no dye control employed foliar application of water only. The testswere conducted with all of the testing on the buffer alone, the amineoxide alone and the buffered amine oxide system of the present inventionin the concentration of 200:1.

The tests were monitored at 24 hours with the results presented in thelast column of Table 7 in percentage values. The concentrations of eachof the insecticides remained constant for the first nine tests wereincreased for the tenth test and were further increased for the eleventhtest. The first group of tests involving no insecticides. The test withonly insecticide produced a value of 41. When the no insecticide testswere performed with no amine oxide for CO₃ and PO₄, the values wererespectively 32.5 and 42.5. With the amine oxide and no buffer, thetests results were 41.5 and 48. With the use of the buffered amine oxideof the present invention, buffer CO₃ produced damage of only 28.0 and47.5, respectively for carbon lengths 12 and 1218. Buffer PO₄ producedvalues of 45.0 and 60.0.

The values for no water control and no dye control were respectively55.0 and 45.5.

In the test involving the insecticide Chlorantranilopril, at 60 ppm,with no amine oxide, the values were respectively 13.5 and 9.0. Withamine oxide but no buffer, the values were 9.0 and 5.5 respectively. Inthe preferred buffered amine oxide system of the present invention, thevalues for CO₃ were 2.5 and 2.5 for carbon lengths 12 and 1218. For PO₄,the values were 4.0 and 0, respectively for carbon lengths 12 and 1218.

When the insecticide was increased 50% to 90 ppm, the damage value was8.2 and when it was increased to 120 ppm, the damage value was 8.5.These tests show that the preferred buffered amine oxide system producedsuperior results to even the greatly increased concentration of theinsecticide showing the economic advantage of using less while achievingapplicant's successful results.

With respect to Acephate, the damage where the buffered amine oxidesystem of the invention was employed, ranged from 1.0 to 11.5 which wasdramatically superior to the other two categories, i.e., no amine oxideand no buffer. With the no amine oxide, the values were 31.0 and 20.0and with the no buffer, the values were 28.0 and 36.0. Increasing theconcentration of the Acephate to 105 ppm and 140 ppm still showedincreased damage of 16.5 and 13.0, respectively, as compared withapplicant's preferred buffered amine oxide system.

When the insecticide concentration of 105 ppm and 140 ppm was employedthe results were respectively 16.5 and 13.0 which was not as good as thebuffered amine oxide system of the present invention. It is noted thatas to the Chlorantranilopril and Acephate, the buffered amine oxidesystem of the present invention was superior to even increasedquantities of the insecticide. As a result, superior inhibition ofdamage was achieved while employing less of the insecticide.

The tests involving the Methoxyfenozide showed with the two preferredbuffers, damages ranging from 4.5 to 9.0 as compared with the testsinvolving no amine oxide or no buffer in which damages ranged from 13.0to 29.5. Increasing the insecticide concentration to 150 ppm and 200 ppmresulted in 43.0 and 23.5 damage values which was substantially higherthan the preferred buffered amine oxide system which produced valuesvery substantially lower.

With the Spinosad tests, the range of damage with the preferred buffersand 12 and 1218 carbon lengths ranged from 6.5 to 12.5 while the testslacking either amine oxide or a buffer had a range of 17 to 24.5.

Even when the concentration of the Spinosad was increased respectivelyto 45 and 60, the damages where 17.0 and 19.0 which exceeded bysubstantial amount the damage employing the system of the presentinvention.

With Permethrin, the damage employing the buffered amine oxide system ofthe invention ranged from 21.0 to 28.0 while for the other twocategories involving no amine oxide or no buffer, the damage ranged from72.0 to 83.0 which was very substantially above the tests involving thesystem of the invention. When the Permethrin was increased from 10 partsper million to 15 ppm and 20 ppm, the results, respectively, were 78.0and 90.0. This once again confirms the substantial advantage of reducingthe amount of insecticide use while achieving superior results throughuse of the buffered amine oxide system.

With the tests involving Indoxacarb, the range of damage employing thesystem of the present invention was 7.0 to 8, while the other testsinvolving either no amine oxide or no buffer ranged from 25.5 to 47.Increasing the concentration of Indoxacarb to tests involving 75 ppm and100 ppm produced results of 20.0 and 12.0 which, despite the increase ininsecticide, were inferior to the results produced by the presentinvention.

It will be appreciated, therefore, that the extensive tests reported inTable 7 establish synergism between the components of the presentinvention which produces superior results while employing lessinsecticide.

TABLE 8 Buffered Amine Oxide System Buffer Number & Amine Oxide PercentLepidopteran Product No Amine Donor or letter Damage to ConcentrationOxide No Buffer CO3 PO4 Romaine Lettuce^((1, 4)) Insecticide PPM CO3 PO412 1218 12 1218 12 1218 24 hr 48 hr 72 hr No insecticide 0 70.0 100.0100.0 No insecticide 0 200:1 80.0 99.0 100.0 No Insecticide 0 200:1 61.5100.0 100.0 No insecticide 0 200:1 55.0 93.0 100.0 No Insecticide 0200:1 54.0 90.5 100.0 No Insecticide 0 200:1 40.5 81.5 100.0 NoInsecticide 0 200:1 34.0 78.0 100.0 No Insecticide 0 200:1 32.0 66.0100.0 No Insecticide 0 200:1 21.0 64.5 100.0 No Insecticide 0 60.0 90.0100.0 (No water Control) No Insecticide 0 45.0 100.0 100.0 (No DyeControl) Chlorantranilopril 60 4.5 9.0 9.0 Chlorantranilopril 60 200:113.0 17.5 19.5 Chlorantranilopril 60 200:1 14.0 22.5 24.5Chlorantranilopril 80 200:1 4.5 8.0 8.5 Chlorantranilopril 60 200:1 10.517.5 18.5 Chlorantranilopril 60 200:1 3.0 5.0 5.0 Chlorantranilopril 60200:1 4.5 12.5 13.0 Chlorantranilopril 60 200:1 1.0 2.0 2.0Chlorantranilopril 60 200:1 6.5 12.5 12.5 Chlorantranilopril 90 7.5 14.015.0 Chlorantranilopril 120 9.5 17.5 17.5 Acephate 70 27.5 47.5 79.5Acephate 70 200:1 50.0 57.5 61.0 Acephate 70 200:1 38.5 53.0 68.5Acephate 70 200:1 27.0 49.5 59.5 Acephate 70 200:1 22.0 52.5 67.0Acephate 70 200:1 34.0 63.5 66.0 Acephate 70 200:1 43.5 55.5 72.0Acephate 70 200:1 29.5 50.5 63.5 Acephate 70 200:1 18.0 32.5 51.0Acephate 105 27.0 44.5 47.0 Acephate 140 29.0 35.5 42.0 Methoxyfenozide100 84.0 94.0 96.0 Methoxyfenozide 100 200:1 96.0 99.5 100.0Methoxyfenozide 100 200:1 100.0 100.0 100.0 Methoxyfenozide 100 200:179.5 82.5 87.0 Methoxyfenozide 100 200:1 72.0 80.5 87.5 Methoxyfenozide100 200:1 42.5 51.5 57.0 Methoxyfenozide 100 200:1 54.5 67.5 73.0Methoxyfenozide 100 200:1 43.0 67.0 73.5 Methoxyfenozide 100 200:1 85.087.0 88.0 Methoxyfenozide 150 100.0 100.0 100.0 Methoxyfenozide 200100.0 100.0 100.0 Spinosad 30 19.0 26.5 59.0 Spinosad 30 200:1 25.5 28.029.0 Spinosad 30 200:1 20.0 28.5 33.0 Spinosad 30 200:1 30.5 35.5 36.0Spinosad 30 200:1 15.0 21.0 28.0 Spinosad 30 200:1 14.0 38.0 49.5Spinosad 30 200:1 6.5 18.5 24.0 Spinosad 30 200:1 10.5 29.5 35.5Spinosad 30 200:1 13.0 22.0 29.5 Spinosad 45 12.0 23.5 36.0 Spinosad 6024.5 34.5 36.5 Permethrin 10 85.5 100.0 100.0 Permethrin 10 200:1 53.597.5 100.0 Permethrin 10 200:1 28.5 79.0 100.0 Permethrin 10 200:1 17.060.0 89.0 Permethrin 10 200:1 24.0 95.0 100.0 Permethrin 10 200:1 23.567.0 91.0 Permethrin 10 200:1 3.0 10.5 21.0 Permethrin 10 200:1 2.0 4.55.0 Permethrin 10 200:1 1.5 3.0 3.0 Permethrin 15 0.0 0.5 0.5 Permethrin20 1.5 4.0 4.5 Indoxacarb 50 19.5 68.5 88.0 Indoxacarb 50 200:1 21.529.0 37.5 Indoxacarb 50 200:1 22.5 25.0 32.5 Indoxacarb 50 200:1 45.555.0 61.5 Indoxacarb 50 200:1 44.5 68.0 71.0 Indoxacarb 50 200:1 33.546.5 57.5 Indoxacarb 50 200:1 61.0 63.5 71.0 Indoxacarb 50 200:1 26.550.5 57.0 Indoxacarb 50 200:1 19.0 34.5 34.5 Indoxacarb 75 32.0 38.072.0 Indoxacarb 100 25.0 35.5 39.5

In the tests reported in Table 8 pages 29-32), romaine lettuce leafdiscs ⅝″ in diameter (L. sativa) were dipped in the treatment solutionfor about one second per disc. Infestation was provided by eightlepidopteran larvae at the 3^(rd) to 4^(th) instar development percontainer. Four cabbage loopers (Trichoplusia ni) and four beetarmyworms (Spodoptera exigua) were employed in infestation. Thecontainers were placed in a dark humidity cabinet at 15° C. and 80%relative humidity. Visual observations of the average percent damage wastaken at 24, 48 and 72 hours after infestation. Damage evaluation was by5% increments over the total disc area.

In the tests results provided in Table 8, the identity andconcentrations of the insecticide was identical to the tests resultsreported in Table 7. The concentration of 200:1 was employed for the noamino oxide, no buffer and buffered amine oxide system. This series oftests, however, reported how the percent damage changed with time at therespective 24, 48 and 72 hour intervals.

With respect to the tests when no insecticide or no amine oxide or nobuffer was employed, while the changes between 24 hour and 48 hourmeasurements varied, at 72 hours, there was 100 percentage damage. Thesame is true with respect to the no water control and no dye control.

Continuing with the Table 8 analysis, the Chlorantranilopril performancewith the CO₃ and PO₄ formulations and 12 carbon length and 1218 carbonlength had a range of 2 to 13 after 72 hours. When the concentration ofChlorantranilopril was increased to 90 and 120, respectively, theresults after 72 hours were 15.0 and 17.5. Even at the enlargedconcentration of Chlorantranilopril the buffered amine oxides in boththe 12 and 1218 lengths produced superior performance to the use of thepesticide alone. With the increased concentration to 90 ppm and 120 ppm,Chlorantranilopril showed damage of 15.0 and 17.50 percent whichconfirms the superiority of applicant's in terms of achieving betterresults using less of the insecticide.

With Acephate, the buffered amine oxide system of the present inventionafter 72 hours the Acephate without using the buffered amine oxideexperienced damage in the range of 59.5 through 79.5. This is to becontrasted with the buffered amine oxide tests at length 12 and 1218 ofapplicant's two buffered amine oxides which had damage in range of 51through 72.

With the Methoxyfenozide, the ranges for the buffered amine oxide systemafter 72 hours were 57.0 to 88.0 which was a substantial improvementover the no amine oxide and no buffer. The Methoxyfenozide atconcentrations of 100 without the amine oxide presented after 72 hoursdamage in the range of 87.5 to 100 and with the increased concentrationof 150 to 200, 100 percent damage.

The Spinosad employed alone had a range of 28 to 59 damage. The rangefor the preferring amine oxide with Spinosad, at 72 hours was 29.5 to49.5. The increased usage of Spinosad alone increased concentration ofSpinosad alone produced results of 36.0 and 36.5.

With respect to Permethrin, applicant's buffered amine oxide systemafter 72 hours showed damage in the range of 3.0 to 91.0 as comparedwith the damage figures of 89.0 through 100% for the no amine and nobuffer test. The increased concentration to 15 ppm and 20 ppm resultedin damage respectively as 0.5 and 4.5 percent.

With the Indoxacarb tests at 72 hours, applications damage valuesemploying the buffered amine oxide ranged from 34.5 to 57.5 and with theno amine oxide and no buffer results were in the range of 32.5 to 88.The increased concentrations of the insecticide to 75 ppm and 100 ppmproduced 72.0 and 39.5, respectively, damage which, in general, weresimilar to applicant's system which employed substantially lessinsecticide.

As will be apparent from the foregoing, extensive testing with a largenumber of different fungicides and insecticides showed by thecomparative data that the buffered amine oxide system achieved asynergistic effect and improved results in terms of resisting damage toliving plants. The buffered amine oxide system additives of the presentinvention may be employed in many ways such as mixing as tank blendswith insecticide or incorporation into insecticide formulations.

It will be appreciated, therefore, that both in connection withfungicide tests and insecticide tests, neither the insecticide norfungicide employed alone achieved any meaningful reduction in stainingfungi or gypsy moth caterpillar in the lower concentrations of thematerial. Similarly, the buffered amine oxide system, when used alone,produced no significant reduction in staining fungi or gypsy mothcaterpillar damage. When, however, the fungicide was used at lower partsper million in combination with the buffered amine oxide systems, therewas, due to synergism, a substantial reduction or elimination ofstaining fungi. Similarly, when the insecticide was used in lowerconcentrations in combination with buffered amine oxide systems, therewas substantial reduction or elimination of gypsy moth caterpillardamage.

It will be appreciated that the extensive additional tests regarding awide variety of fungicides measured against staining fungi covering astem wound of red oak seedlings and the additional testing of a widerange of insecticides in both testing against living romaine lettuceplants and romaine lettuce leaf discs challenged with lepidopteranlarvae; cabbage loopers and beet army worms provided clear evidence ofthe synergistic effect of the combination contained in applicant'sbuffered amine oxide system buffers as contrasted with either nofungicide or insecticide or omission of the amine oxide or omission ofthe buffer.

While particular embodiments of this invention have been describedherein for purposes of illustration, it will be evident to those skilledin the art that numerous variations of the details of the presentinvention may be made without departing from the invention as defined inthe appended claims.

What is claimed is:
 1. A solution for resisting destruction of livingplants comprising a buffered amine oxide admixed with a materialselected from the group consisting of an insecticide and a fungicide,said solution being characterized by the property of synergisticallyeffecting greater resistance to plant destruction than said bufferedamine oxide and either said insecticide or said fungicide employedalone, said buffered amine oxide having a dual buffer, said bufferedamine oxide having a pH of 6.5 to 10.5, said buffered amine oxide beingpresent in a concentration of 200:1 to 400:1 on a total solution volumebasis.
 2. The solution of claim 1 including said solution having afungicide present in an amount of 50 ppm on a total solution weightbasis.
 3. The solution of claim 1 including said solution having aninsecticide present in an amount of 10 ppm on a total solution weightbasis.
 4. The solution of claim 1 including said solution having saidinsecticide present in an amount of 10 to 100 ppm.
 5. The solution ofclaim 2 including said buffered amine oxide having a carbon lengthselected from the group consisting of (a) 12 carbon length amine oxideand (b) a mixture of 12 and 18 carbon length amine oxide.
 6. Thesolution of claim 5 including said buffered amine oxide having a carbonlength of a mixture of 12 and 18 carbon length amine oxides.
 7. Thesolution of claim 6 including said 12 carbon length amine oxide on aweight basis being present in an amount of 1.3 to 2.0 times the amountof 18 carbon length amine oxide.
 8. The solution of claim 6 includingsaid 12 carbon length amine oxide on a weight basis being present in anamount of 1.5 to 1.8 times the amount of 18 carbon length amine oxide.9. The solution of claim 1 including said buffered amine oxide having apH of 7 to
 9. 10. The solution of claim 1 including said buffered amineoxide being 12 carbon length amine oxide and said buffer system selectedfrom the group consisting of (a) Potassium Phosphate Monobasic/PotassiumPhosphate Dibasic and (b) Potassium Bicarbonate/Potassium Carbonate. 11.The solution of claim 1 including said buffered amine oxide having amixture of 12 carbon length amine oxide and 18 carbon length amineoxide, and said buffer selected from the group consisting of (a)Potassium Phosphate Monobasic/Potassium Phosphate Dibasic and (b)Potassium Bicarbonate/Potassium Carbonate.
 12. The solution of claim 1including said buffered amine oxide is Potassium PhosphateMonobasic/Potassium Phosphate Dibasic.
 13. The solution of claim 1including said buffered amine oxide is Potassium Bicarbonate/PotassiumCarbonate.
 14. A method for resisting destruction of living plantscomprising providing a solution having a buffered amine oxide admixedwith a material selected from the group consisting of an insecticide anda fungicide, and applying said solution to effect synergistic protectionof said living plants against a pest selected from the group consistingof insects and fungi through said application of said solutionsynergistically effecting greater resistance to said plant deteriorationthan said buffered amine oxide and either said insecticide or saidfungicide employed alone would achieve, employing a dual buffer in saidbuffered amine oxide, said buffered amine oxide having a pH of 6.5 to10.5.
 15. The method of claim 14 including said solution with saidbuffered amine oxide being present in an amount of 400:1 to 200:1 on avolume to volume basis based on total solution.
 16. The method of claim14 including said solution having a fungicide present in an amount of 50ppm on a total solution weight basis.
 17. The method of claim 14including said solution having an insecticide present in an amount of 10ppm on a total solution weight basis.
 18. The method of claim 14including said solution having insecticide in an amount of 10 to 100 ppmon a solution total weight basis.
 19. The method of claim 14 includingsaid buffered amine oxide having a carbon length selected from the groupconsisting of (a) 12 carbon length amine oxide and (b) a mixture of 12and 18 carbon length amine oxides.
 20. The method of claim 19 includingsaid 12 carbon length amine oxide on a weight basis being present in anamount of 1.3 to 2.0 times the amount of 18 carbon length amine oxide.21. The method of claim 19 including said 12 carbon length amine oxideon a weight basis being present in an amount of 1.5 to 1.8 times theamount of 18 carbon length amine oxide.
 22. The method of claim 14including said solution containing a buffered amine oxide having a pH of6.5 to 10.5.
 23. The method of claim 22 including said solutioncontaining a buffered amine oxide having a pH of 7 to
 9. 24. The methodof claim 14 including said buffered amine oxide being 12 carbon lengthamine oxide, and a buffer amine oxide selected from the group consistingof (a) Potassium Phosphate Monobasic/Potassium Phosphate Dibasic and (b)Potassium Bicarbonate/Potassium Carbonate.
 25. The method of claim 14including said buffered amine oxide is Potassium PhosphateMonobasic/Potassium Phosphate Dibasic.
 26. The method of claim 14including said buffered amine oxide is Potassium Bicarbonate/PotassiumCarbonate.
 27. The method of claim 14 including said buffered amineoxide having a mixture of 12 carbon length amine oxide and 18 carbonlength amine oxide and said buffers selected from the group consistingof (a) Potassium Phosphate Monobasic/Potassium Phosphate Dibasic and (b)Potassium Bicarbonate/Potassium Carbonate, and said buffered amine oxidehaving a concentration of 200:1 to 400:1 on a volume to volume basis.28. A solution for resisting destruction of living plants comprising adual buffered amine oxide admixed with an insecticide, and said solutionbeing characterized by the property of synergistically effecting greaterresistance to plant destruction than said buffered amine oxide and saidinsecticide employed alone, said buffered amine oxide having a pH of 6.5to 10.5.
 29. The solution of claim 28 including said insecticide beingan insecticide selected from the group consisting of Chlorantranilopril,Acephate, Methoxyfenozide, Spinosad, Permethrin and Indoxacarb.
 30. Thesolution of claim 29 including said buffered amine oxide having a carbonlength selected from the group consisting of (a) 12 carbon length amineoxide and (b) a mixture of 12 and 18 carbon length amine oxide.
 31. Thesolution of claim 29 including said buffered amine oxide being 12 carbonlength amine oxide, and said buffer system selected from the groupconsisting of (a) Potassium Phosphate Monobasic/Potassium PhosphateDibasic and (b) Potassium Bicarbonate/Potassium Carbonate.
 32. Thesolution of claim 29 including said buffered amine oxide having amixture of 12 carbon length amine oxide, and said buffer 18 carbonlength amine oxide and said buffer selected from the group consisting of(a) Potassium Phosphate Monobasic/Potassium Phosphate Dibasic and (b)Potassium Bicarbonate/Potassium Carbonate.
 33. The solution of claim 29including said buffered amine oxide is Potassium PhosphateMonobasic/Potassium Phosphate Dibasic.
 34. The solution of claim 29including said buffered amine oxide is Potassium Bicarbonate/PotassiumCarbonate.
 35. A method of resisting destruction of living plantscomprising providing a solution having a dual buffered amine oxideadmixed with an insecticide, and applying said solution to said livingplant to effect synergistic protection of said living plants againstinsects, said buffered amine oxide having a pH of 6.5 to 10.5.
 36. Themethod of claim 35 including said insecticides being an insecticideselected from the group consisting of Chlorantranilopril, Acephate,Methoxyfenozide, Spinosad, Permethrin and Indoxacarb.
 37. The method ofclaim 36 including said buffered amine oxide having a carbon lengthselected from the group consisting of (a) 12 carbon length amine oxideand (b) a mixture of 12 and 18 carbon length amine oxide.
 38. The methodof claim 36 including said buffered amine oxide being 12 carbon lengthamine oxide, and said buffer system selected from the group consistingof (a) Potassium Phosphate Monobasic/Potassium Phosphate Dibasic and (b)Potassium Bicarbonate/Potassium Carbonate.
 39. The method of claim 36including said buffered amine oxide having a mixture of 12 carbon lengthamine oxide, said buffer 18 carbon length amine oxide, and said bufferselected from the group consisting of (a) Potassium PhosphateMonobasic/Potassium Phosphate Dibasic and (b) PotassiumBicarbonate/Potassium Carbonate.
 40. The method of claim 36 includingsaid buffered amine oxide is Potassium Phosphate Monobasic/PotassiumPhosphate Dibasic.
 41. The method of claim 36 including said bufferedamine oxide is Potassium Bicarbonate/Potassium Carbonate.
 42. A solutionfor resisting destruction of living plants comprising a dual bufferedamine oxide admixed with a fungicide, and said solution beingcharacterized by the property of synergistically effecting greaterresistance to plant destruction than said buffered amine oxide and saidfungicide employed alone, said buffered amine oxide having a pH of 6.5to 10.5.
 43. The solution of claim 42 including said fungicides being afungicide selected from the group consisting of Thiabendazole,Fludioxonil, Azoxystrobin, Chlorothalonil, Propiconazole, Mancozeb,Vinclozolin and Mefenoxam.
 44. The solution of claim 43 including saidbuffered amine oxide having a carbon length selected from the groupconsisting of (a) 12 carbon length amine oxide and (b) a mixture of 12and 18 carbon length amine oxide.
 45. The solution of claim 43 includingsaid buffered amine oxide being 12 carbon length amine oxide, and saidbuffer system selected from the group consisting of (a) PotassiumPhosphate Monobasic/Potassium Phosphate Dibasic and (b) PotassiumBicarbonate/Potassium Carbonate.
 46. The solution of claim 43 includingsaid buffered amine oxide having a mixture of 12 carbon length amineoxide and 18 carbon length amine oxide, and said buffer selected fromthe group consisting of (a) Potassium Phosphate Monobasic/PotassiumPhosphate Dibasic and (b) Potassium Bicarbonate/Potassium Carbonate. 47.The solution of claim 43 including said buffered amine oxide isPotassium Phosphate Monobasic/Potassium Phosphate Dibasic.
 48. Thesolution of claim 43 including said buffered amine oxide is PotassiumBicarbonate/Potassium Carbonate.
 49. A method of resisting destructionof living plants comprising providing a solution having a dual bufferedamine oxide admixed with a fungicide, and applying said solution to saidliving plant to effect synergistic protection of said living plantsagainst fungi, said buffered amine oxide having a pH of 6.5 to 10.5. 50.The method of claim 49 including said fungicides being a fungicideselected from the group consisting of Chlorantranilopril, Acephate,Methoxyfenozide, Spinosad, Permethrin and Indoxacarb.
 51. The method ofclaim 50 including said buffered amine oxide having a carbon lengthselected from the group consisting of (a) 12 carbon length amine oxideand (b) a mixture of 12 and 18 carbon length amine oxide.
 52. The methodof claim 50 including said buffered amine oxide being 12 carbon lengthamine oxide, and said buffer system selected from the group consistingof (a) Potassium Phosphate Monobasic/Potassium Phosphate Dibasic and (b)Potassium Bicarbonate/Potassium Carbonate.
 53. The method of claim 50including said buffered amine oxide having a mixture of 12 carbon lengthamine oxide and 18 carbon length amine oxide, and said buffer selectedfrom the group consisting of (a) Potassium Phosphate Monobasic/PotassiumPhosphate Dibasic and (b) Potassium Bicarbonate/Potassium Carbonate. 54.The method of claim 50 including said buffered amine oxide is PotassiumPhosphate Monobasic/Potassium Phosphate Dibasic.
 55. The method of claim50 including said buffered amine oxide is PotassiumBicarbonate/Potassium Carbonate.